JP2013147637A - ETHYLENE-α-OLEFIN-NON-CONJUGATED POLYENE COPOLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-α-olefin-non-conjugated polyene copolymer excellent in roller kneading processability and extrudability.SOLUTION: The ethylene-α-olefin-non-conjugated polyene copolymer satisfies the following conditions (A), (B), (C), (D) and (E). (A) The limiting viscosity [η] is 0.5-1.8 dL/g. (B) When the total of the content of ethylene units and the content of α-olefin units is taken as 100 mol%, the content of ethylene units is 50-90 mol% and the content of α-olefin units is 50-10 mol%. (C) The iodine number is 1-50. (D) The ratio of the tanδ at 100°C and 2 cpm to the tanδ at 100°C and 1,000 cpm is 1.0-1.7. (E) The ratio of the Z-average molecular weight to the number-average molecular weight is 15-25, and the ratio of the weight-average molecular weight to the number-average molecular weight is 3-5.

Description

  The present invention relates to an ethylene-α-olefin-nonconjugated polyene copolymer.

For automobiles, motorbikes, industrial machinery, construction machinery, agricultural machinery, etc., radiator hose for cooling the engine, drain hose for radiator overflow, heater hose for indoor heating, air conditioning drain hose, wiper water hose, roof drain hose, professional Various rubber hoses such as lactose hose are attached.
As raw rubbers used for rubber hoses, for example, Patent Documents 1 and 2 describe ethylene-α-olefin-nonconjugated polyene copolymers.

JP 2004-285324 A JP 2011-174002 A

However, the conventional ethylene-α-olefin-nonconjugated polyene copolymer has a roll kneading processability when the polymer and auxiliary materials are roll kneaded to prepare a polymer composition, and the polymer composition. Both were not fully satisfied with the extrudability at the time of extrusion molding into a molded body such as a hose.
Under such circumstances, the problem to be solved by the present invention is to provide an ethylene-α-olefin-nonconjugated polyene copolymer excellent in roll kneading processability and extrusion processability.

The present invention is an ethylene-α-olefin-nonconjugated polyene copolymer containing an ethylene unit, an α-olefin unit, and a nonconjugated polyene unit, which has the following requirements (A), (B), (C), (D ) And (E). An ethylene-α-olefin-nonconjugated polyene copolymer is satisfied.
(A): Intrinsic viscosity [η] is 0.5 to 1.8 dl / g.
(B): When the total content of the ethylene unit and the α-olefin unit is 100 mol%, the ethylene unit content is 50 to 90 mol%, and the α-olefin unit content is 50 to 10 mol%.
(C): The iodine value is 1-50.
(D): The ratio of tan δ at 100 ° C. and 2 cpm to tan δ at 100 ° C. and 1000 cpm is 1.0 to 1.7.
(E): The ratio of the Z-average molecular weight to the number average molecular weight is 15 to 25, and the ratio of the weight average molecular weight to the number average molecular weight is 3 to 5.

  According to the present invention, an ethylene-α-olefin-nonconjugated polyene copolymer excellent in roll kneading processability and extrusion processability can be provided.

The present invention relates to an ethylene-α-olefin-nonconjugated polyene copolymer comprising an ethylene unit, an α-olefin unit and a nonconjugated polyene unit. In the present invention, the term “monomer name + unit” such as “ethylene unit”, “α-olefin unit”, and “non-conjugated polyene unit” means “monomer unit based on the monomer”.
The α-olefin of the ethylene-α-olefin-nonconjugated polyene copolymer is preferably an α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1 -Linear α-olefins such as heptene, 1-octene, 1-nonene, 1-decene; branched such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene An α-olefin is exemplified. One or more of these are used.
The α-olefin is preferably propylene or 1-butene, more preferably propylene.

  Examples of the non-conjugated polyene of the ethylene-α-olefin-non-conjugated polyene copolymer include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1,5. -Chain non-conjugated dienes such as heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetraindene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5 -(7-octenyl) -2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5- Cyclic non-conjugated dienes such as lopyridene-2-norbornene, 5-butylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene- 3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 6,10-dimethyl-1,5,9-undeca Triene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, 13-ethyl-9-methyl-1,9,12-pentadecatriene, 8, Tris such as 14,16-trimethyl-1,7,14-hexadecatriene, 4-ethylidene-12-methyl-1,11-pentadecadiene En. One or more of these are used. The non-conjugated polyene is preferably 5-alkylidene-2-norbornene such as 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, 5-butylidene-2-norbornene; 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) ) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene and the like are preferable, and 5-alkylidene-2-norbornene is more preferable. preferable.

  As the ethylene-α-olefin-nonconjugated polyene copolymer, the α-olefin is propylene, and the nonconjugated polyene is selected from a compound group consisting of 5-alkylidene-2-norbornene and 5-alkenyl-2-norbornene. A copolymer that is at least one compound is preferred.

  Examples of the ethylene-α-olefin-nonconjugated polyene copolymer include ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, and ethylene-propylene-5-vinyl. 2-norbornene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-dicyclopentadiene copolymer, ethylene-1-butene-5-vinyl-2- Mention may be made of norbornene copolymers.

  The intrinsic viscosity [η] of the ethylene-α-olefin-nonconjugated polyene copolymer is 0.5 dl / g or more and 1.8 dl / g or less. The intrinsic viscosity [η] is preferably 1.0 dl / g or more, more preferably 1.3 dl / g or more, and further preferably 1.4 dl / g in order to improve roll kneading processability. . Moreover, in order to improve extrudability, it is preferably 1.7 dl / g or less. The intrinsic viscosity [η] is measured at 135 ° C. in tetralin.

  The ethylene-α-olefin-nonconjugated polyene copolymer has an ethylene-based monomer unit (ethylene unit) content of 50 mol% to 90 mol%, and an α-olefin-based monomer unit (α-olefin). The content of (unit) is 10 mol% or more and 50 mol% or less. In order to improve roll kneading workability, the ethylene unit content is preferably 55 mol% or more, the α-olefin unit content is 45 mol% or less, and more preferably, the ethylene unit content is 58 mol%. %, The content of α-olefin units is 42 mol% or less, more preferably the content of ethylene units is 60 mol% or more, and the content of α-olefin units is 40 mol% or less. In order to enhance the extrudability, the ethylene unit content is preferably 80 mol% or less, the α-olefin unit content is 20 mol% or more, and more preferably, the ethylene unit content is 75 mol%. Hereinafter, the content of α-olefin units is 25 mol% or more, more preferably the content of ethylene units is 70 mol% or less, and the content of α-olefin units is 30 mol% or more. However, the total of the ethylene unit content and the α-olefin unit content is 100 mol%. The content of ethylene units and the content of α-olefin units are measured by infrared spectrophotometry.

  The iodine value (unit: g / 100 g polymer) of the ethylene-α-olefin-nonconjugated polyene copolymer is 1 or more and 50 or less. The iodine value is preferably 5 or more, more preferably 10 or more, and more preferably 12 or more in order to improve roll kneading processability. Moreover, in order to improve extrusion processability, Preferably it is 40 or less, More preferably, it is 35 or less, More preferably, it is 30 or less.

  The ratio of tan δ at 100 ° C. and 2 cpm to tan δ at 100 ° C. and 1000 cpm of the ethylene-α-olefin-nonconjugated polyene copolymer, ie tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm)) 1.0 or more and 1.7 or less. The ratio is preferably 1.6 or less, and more preferably 1.5 or less, in order to improve the extrusion processability. Here, tan δ is the ratio of the shear loss modulus to the shear storage modulus (shear loss modulus / shear storage modulus), and is measured by a viscoelasticity measuring device at a temperature of 100 ° C. and a strain of 13.95%. The

  The ratio of the Z-average molecular weight (Mz) to the number-average molecular weight (Mn) of the ethylene-α-olefin-nonconjugated polyene copolymer, that is, Mz / Mn is 15 or more and 25 or less. Mz / Mn is preferably 17 or more in order to improve roll kneading processability, and preferably 22 or less in order to improve extrusion processability. Z-average molecular weight (Mz) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC).

  The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ethylene-α-olefin-nonconjugated polyene copolymer, that is, Mw / Mn is 3 or more and 5 or less. Mw / Mn is preferably 4 or more in order to improve roll kneading processability. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by a gel permeation chromatography (GPC) method.

As a method for producing the ethylene-α-olefin-nonconjugated polyene copolymer of the present invention, a polymerization catalyst using a vanadium compound and an organoaluminum compound as a polymerization catalyst component is used in a hydrocarbon compound solvent under the following conditions (a ), (B) and (c), and a method of copolymerizing ethylene, α-olefin and non-conjugated polyene.
(A) The molar ratio (number of moles of organoaluminum compound / number of moles of vanadium compound) of the amount of organoaluminum compound used relative to the amount of vanadium compound used is 0.1 to 2.0.
(B) The polymerization temperature is 50 to 80 ° C.
(C) The amount of hydrogen supplied to the polymerization reactor is 0.001 to 0.1 NL per 1 kg of the solvent supplied to the polymerization reactor.
(D) The amount of the vanadium compound supplied to the polymerization reactor is 0.02 to 0.2 parts by weight per 100 parts by weight of the solvent supplied to the polymerization reactor.

Examples of the vanadium compound in the production _{process, VOCl 3, VO (OCH 3} ) 0.5 Cl 2.5, VO (OC 2 H 5) 0.5 C l2.5, VO (O (n-C 3 H 7)) 0.5 Cl 2.5, _{VO (O (n-C 4} H 9)) 0.5 Cl 2.5, VO (O (n-C 5 H 11)) 0.5 Cl 2.5, VO (O (n-C 6 H 13)
) _0.5 Cl _2.5 , VO (O (n—C ₇ H ₁₅ )) _0.5 Cl _2.5 , VO (O (n—C ₈ H ₁₇ )) _0.5 Cl _2.5 , VO (OCH ₃ ) _0.8 Cl _2.2 , VO (OC _{2 H 5) 0.8 Cl 2.2, VO} (O (n-C 3 H 7)) 0.8 Cl 2.2, VO (O (n-C 4 H 9)) 0.8 Cl 2.2, VO (O (n-C 5 H 11) _0.8 Cl _2.2 , VO (O (n—C ₆ H ₁₃ )) _0.8 Cl _2.2 , VO (O (n—C ₇ H ₁₅ )) _0.8 Cl _2.2 , VO (O (n—C ₈ H ₁₇ )) _0.8 Cl _2.2 , VO (OCH ₃ ) Cl ₂ , VO (OC ₂ H ₅ ) Cl ₂ , VO (O (n—C ₃ H ₇ )) Cl ₂ , VO (O (n—C ₄ H ₉ )) Cl ₂ , VO (O (n-C 5 H 11)) Cl 2, VO (O (n-C 6 H 13)) Cl 2, VO (O (n-C 7 H 15)) Cl 2, VO (O ( _{n-C 8 H 17))} Cl 2, VO (OCH 3) 1.5 Cl 0.5, VO (OC 2 H 5) 1.5 Cl 0.5, _{O (O (n-C 3} H 7)) 1.5 Cl 0.5, VO (O (n-C 4 H 9)) 1.5 Cl 0.5, VO (O (n-C 5 H 11)) 1.5 Cl 0.5, VO ( _{O (n-C 6 H 13} )) 1.5 Cl 0.5, VO (O (n-C 7 H 15)) 1.5 Cl 0.5, VO (O (n-C 8 H 17)) 1.5 Cl 0.5, etc. VO ( OR) _m Cl _n [wherein R represents an alkyl group having 1 to 10 carbon atoms, and m and n are numbers satisfying m + n = 3, 0 ≦ m <3, and 0 <n ≦ 3. ] The compound represented by this can be mention | raise | lifted. Preferably, VOCl ₃ , VO (OC ₂ H ₅ ) _0.5 Cl _2.5 , VO (OC ₂ H ₅ ) _0.8 Cl _2.2 , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) _1.5 Cl _0.5, etc. VO (OC ₂ H ₅ ) _r Cl _s [wherein r and s are numbers satisfying r + s = 3, 1 ≦ r <3 and 0 <s ≦ 2. ], More preferably VOCl ₃ .

As the organoaluminum compound in the above production method, (C ₂ H ₅ ) ₂ AlCl, (n-C ₄ H ₉ ) ₂ AlCl, (iso-C ₄ H ₉ ) ₂ AlCl, (n-C ₆ H ₁₃ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (n-C ₄ H ₉ ) _1.5 AlCl _1.5 , (iso-C ₄ H ₉ ) _1.5 AlCl _1.5 , (n-C ₆ H ₁₃ ) _1.5 AlCl _1.5 , C ₂ R _t AlCl _u such as H ₅ AlCl ₂ , (n-C ₄ H ₉ ) AlCl ₂ , (iso-C ₄ H ₉ ) AlCl ₂ , (n-C ₆ H ₁₃ ) AlCl ₂ , wherein R is carbon An alkyl group having 1 to 10 atoms is represented, and t and u are numbers satisfying t + u = 3, 0 <t ≦ 3, and 0 ≦ u <3. ] The compound represented by this can be mention | raise | lifted. Preferably, R _x AlCl _y [wherein R represents an alkyl group having 2 to 6 carbon atoms, and x and y are numbers satisfying x + y = 3, 1 ≦ x ≦ 2 and 1 ≦ y ≦ 2. is there. And more preferably (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 .

  The polymerization catalyst is preferably a catalyst obtained by contacting a vanadium compound and an organoaluminum compound in the absence of alcohol.

  Examples of the hydrocarbon compound used in the solvent include aliphatic hydrocarbon compounds such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane.

  The molar ratio of the amount of the organoaluminum compound used to the amount of the vanadium compound used (the number of moles of the organoaluminum compound / the number of moles of the vanadium compound) is preferably 0.1 to 2.0, more preferably 0.8. It is 5-1.8, More preferably, it is 0.8-1.7. In order to reduce tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) or to reduce the intrinsic viscosity [η], it is preferable to reduce the molar ratio. In order to increase Mz / Mn and Mw / Mn, it is preferable to decrease the molar ratio.

  The polymerization temperature is preferably 50 to 80 ° C, more preferably 55 to 60 ° C. In order to decrease tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) or increase Mz / Mn and Mw / Mn, it is preferable to increase the polymerization temperature.

  The polymerization pressure is usually 0.1 to 10 MPa, preferably 0.1 to 5 MPa, and more preferably 0.1 to 3 MPa.

  The amount of hydrogen supplied to the polymerization reactor is preferably 0.001 to 0.1 NL, more preferably 0.005 to 0.05 NL, even more preferably per 1 kg of the solvent supplied to the polymerization reactor. Is 0.01-0.04NL. In order to increase Mz / Mn or increase the intrinsic viscosity [η], it is preferable to reduce the supply amount of the hydrogen.

  The amount of the vanadium compound supplied to the polymerization reactor is preferably 0.02 to 0.2 parts by weight, more preferably 0.03 to 0.1 parts per 100 parts by weight of the solvent supplied to the polymerization reactor. Parts by weight. In order to increase the intrinsic viscosity [η] or increase tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm), it is preferable to increase the amount of the vanadium compound.

  The ethylene-α-olefin-nonconjugated polyene copolymer of the present invention is suitably used as a vulcanized rubber material.

  As a method for preparing the vulcanized rubber, there is a method in which an additive and / or a resin are blended with the ethylene-α-olefin-nonconjugated polyene copolymer as necessary, and vulcanized by heating, electron beam irradiation or the like. can give.

  Examples of the additive include a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a softening agent, a reinforcing agent, a foaming agent, a foaming aid, a stabilizer, and an antifoaming agent.

  As the vulcanizing agent, sulfur, a sulfur compound, an organic peroxide, or the like can be used. As sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used. The amount of sulfur and sulfur-based compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. It is.

  Examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5- (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide . Preferred is dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and more preferred is di-tert-butyl peroxide-3,3,5-trimethylcyclohexane. . The amount of the organic peroxide used is preferably 0.1 to 15 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer.

  Examples of the vulcanization aid used together with sulfur or sulfur-based compounds include metal oxides such as magnesium oxide and zinc oxide. Zinc oxide is preferable. The compounding amount of these vulcanization aids is preferably 1 to 20 parts by weight with 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer.

  Examples of vulcanization aids used with organic peroxides include triallyl isocyanurate, N, N′-m-phenylenebismaleimide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol mono Methacrylate, polypropylene glycol monomethacrylate, 2-ethoxy ether Methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacryloxyethyl phosphate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3- Butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethanetri Meta Relate, trimethylolpropane trimethacrylate, allyl glycidyl ether, N-methylol methacrylamide, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, aluminum methacrylate, zinc methacrylate, calcium methacrylate, magnesium methacrylate, 3 -Chloro-2-hydroxypropyl methacrylate and the like can be mentioned. The compounding amount of these vulcanization aids is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 8 parts by weight, with 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. Part.

  Examples of the vulcanization accelerator include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram tetrasulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, N, N′-dioctadecyl-N, N′-diisopropylthiuram disulfide, N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N -Diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6- Ethyl-4-morpholinothio) benzothiazole, dibenzothiazyl-disulfide, diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotolyl-by-guanide, diphenylguanidine-phthalate, acetaldehyde-aniline reactant, butyraldehyde- Aniline condensate, hexamethylenetetramine, acetaldehyde ammonia, 2-mercaptoimidazoline, thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diortholylthiourea, zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n -Zinc butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyldithiocarbamate Sodium vammin acid, dimethyl dithiocarbamate selenium include diethyl dithiocarbamate tellurium, dibutyl xanthate zinc, and ethylene thiourea. The blending amount of the vulcanization accelerator is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. is there.

  As softeners, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil softeners such as coconut oil; waxes such as tall oil, sub, beeswax, carnauba wax, lanolin, fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; petroleum Examples thereof include synthetic polymer substances such as resins, atactic polypropylene, and coumarone indene resins. The blending amount of the softening agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, still more preferably 50, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. -200 parts by weight.

  Examples of the reinforcing agent include carbon black, silica, calcium carbonate, fine powder talc, fine powder aluminum silicate and the like. Examples of the carbon black include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. These carbon blacks may be surface-treated with a silane coupling agent or the like. The compounding amount of the reinforcing agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, still more preferably 50, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. -200 parts by weight.

  Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide, N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, P, P Sulfonyl hydrazide compounds such as' -oxybis (benzenesulfonylhydrazide) and diphenylsulfone-3,3'-disulfonylhydrazide; calcium azide, 4,4'-diphenyldisulfonylazide, P-toluenesulfur Such as azide compounds such as Niruajido can be mentioned. The blending amount of the foaming agent is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer.

  Examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid; urea or derivatives thereof. The blending amount of the foaming aid is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. .

  Examples of the stabilizer include amine-based anti-aging agents, hindered phenol-based anti-aging agents, and sulfur-based anti-aging agents. The blending amount of the stabilizer is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer.

  An example of an antifoaming agent is calcium oxide. The blending amount of the antifoaming agent is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the ethylene-α-olefin-nonconjugated polyene copolymer. .

  Examples of the resin include polyethylene resin, polypropylene resin, polybutene, poly-4-methyl-pentene-1, polystyrene, polyester, polyamide, polyphenylene ether, and the like. Examples of the polyethylene resin include high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene.

  As a method for preparing a polymer composition by blending an additive and / or a resin with an ethylene-α-olefin-nonconjugated polyene copolymer, a known method can be used. For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, a softener, a reinforcing agent, a stabilizer, and the like and an ethylene-α-olefin-nonconjugated polyene copolymer at a temperature of 80 to 170 ° C. Kneading for 3 to 10 minutes, and then using a roll such as an open roll or a kneader at a temperature of 40 to 80 ° C., if necessary, a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, a foaming agent, etc. And a polymer composition can be prepared by kneading for 5 to 30 minutes. When the kneading temperature in the internal mixer is lower than the decomposition temperature of the vulcanizing agent or blowing agent, the softening agent, reinforcing agent, stabilizer, etc., and the vulcanizing agent, blowing agent, etc. may be kneaded simultaneously. it can.

  In the method of vulcanizing the ethylene-α-olefin-nonconjugated polyene copolymer by heating, heating means such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (hot molten salt bath), etc. A heating tank having a mold can be used. The heating temperature is preferably 150 to 270 ° C., and the heating time is preferably 1 to 60 minutes.

  In the method of vulcanizing the ethylene-α-olefin-nonconjugated polyene copolymer by electron beam irradiation, the energy of the electron beam is preferably 0.1 to 10 MeV, more preferably 0.3 to 2 MeV. . Further, it is preferable to irradiate the ethylene-α-olefin-nonconjugated polyene copolymer with an electron beam so that the absorbed dose is 0.5 to 35 Mrad, and the electron beam so that the absorbed dose is 0.5 to 10 Mrad. Is more preferably irradiated to the ethylene-α-olefin-nonconjugated polyene copolymer.

  Vulcanized rubber is suitably used for rubber hoses. Examples of the rubber hose include a radiator hose, a heater hose, a brake hose, and a brake reservoir hose.

  As a method of manufacturing a rubber hose having a layer made of vulcanized rubber, a softener, a reinforcing agent, a stabilizer, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid are added to an ethylene-α-olefin-nonconjugated polyene copolymer. A polymer composition containing an additive such as an agent is molded into a molded body having a desired shape by a known molding machine (for example, an extrusion molding machine), and the molded body is formed simultaneously with or after the molding. A method of vulcanizing and foaming a molded body by heating the above; a polymer composition containing an additive such as a foaming agent is molded into a molded body having a desired shape by the known molding machine; At the same time or after the molding, there are a method of vulcanizing the molded body by heating the molded body and a method of vulcanizing the molded body by irradiating the molded body with an electron beam.

  Hereinafter, the present invention will be described by way of examples.

[Measurement and evaluation method]
(1) Ethylene unit amount and propylene unit amount The copolymer was formed into a film having a thickness of about 0.1 mm with a hot press machine, and the infrared of the film was measured with an infrared spectrophotometer (IR-810, manufactured by JASCO Corporation). Absorption spectrum was measured. From the infrared absorption spectrum, the literature (characterizing polyethylene by infrared absorption spectrum, Takayama, Usami et al. And Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, Madam S, WF, etc. ) According to the method described, the ethylene unit amount and the propylene unit amount were determined.

(2) Iodine value The copolymer was formed into a film having a thickness of about 0.5 mm by a hot press. The intensity of the peak derived from 5-ethylidene-2-norbornene (absorption peak at 1688 cm-1) of the film was measured by an infrared spectrophotometer. The molar content of the double bond was determined from the peak intensity, and the iodine value was calculated from the molar content.

(3) Mz / Mn and Mw / Mn
By the gel permeation chromatography (GPC) method, under the following conditions (1) to (9), the Z-average molecular weight (Mz), number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymer ) And Mz / Mn and Mw / Mn were determined.
(1) Equipment: Waters 150C
(2) Separation column: Shodex Packed Column A-80M manufactured by Showa Denko KK (3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Sample concentration: about 1mg / 1mL
(7) Sample injection amount: 400 μL
(8) Detector: Differential refraction
(9) Molecular weight reference material: Standard polystyrene

(4) Intrinsic viscosity The intrinsic viscosity was measured in a 135 ° C. tetralin solution using an Ubbelohde viscometer.

(5) tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm)
Using a viscoelasticity measuring device (ALPHA TECHNOLOGIES, RUBBER PROCESS ANALYZER RPA2000P), changing the frequency at a temperature of 100 ° C. and a strain of 13.95%, the tan δ (shear loss modulus and shear storage modulus of the copolymer) Ratio: shear loss modulus / shear storage modulus). The ratio of tan δ at a frequency of 2 cpm and tan δ at a frequency of 1000 cpm was calculated.

(6) Roll kneading workability of polymer composition In step (2) of preparing polymer compositions in Examples and Comparative Examples, the presence or absence of bagging during roll kneading was observed. Those with no bagging were evaluated as “good” and those with bagging were evaluated as “bad”.

(7) Extrusion Processability of Polymer Composition L / D = 16 45 mmφ vent type extruder (manufactured by Nakata Engineering Co., Ltd.), as an extrusion die, as defined in 5.2 Die-ASTM Extension Die of ASTM D2230-90 An extrusion die is set, and the polymer composition is extruded from the die at a screw temperature of 40 ° C., a cylinder temperature of 60 ° C., a die temperature of 80 ° C., and a screw rotation speed of 60 rpm, and the polymer composition is extruded. The speed (cm / min) was measured. The higher the speed, the better the extrudability. The length (cm) per unit time (min) of the extruded elongated polymer composition was defined as the extrusion rate (cm / min).

Example 1
(Preparation of copolymer)
The temperature of a stainless steel polymerization tank equipped with a stirrer is kept at 60 ° C., and 0.461 kg / (hr · L) of hexane and 31.6 g of ethylene per unit time / unit volume of the polymerization tank are stored in the polymerization tank. / (Hr · L), propylene was fed at a rate of 169 g / (hr · L). VOCl ₃ was supplied to the polymerization tank at a rate of 230 mg / (hr · L), ethylaluminum sesquichloride (EASC) at 341 mg / (hr · L), and hydrogen at a rate of 0.013 NL / (hr · L). Further, 5-ethylidene-2-norbornene was supplied to the polymerization tank at a rate of 2.8 g / (hr · L).
The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant.
The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-A).
When EPDM-A was analyzed, the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-A was 0.61 / 0.39, and the iodine value was 14.4 (g / 100 g polymer). Mz / Mn was 19.1, Mw / Mn was 4.2, intrinsic viscosity was 1.60 dl / g, and tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) was 1.40.

(Preparation of polymer composition)
Process (1)
100 parts by weight of EPDM-A, 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 90 parts by weight of FEF carbon black (Asahi Carbon Co., Ltd. Asahi 60G), 5 parts by weight of paraffinic oil ( Diana PW380 manufactured by Idemitsu Kosan Co., Ltd., 2 parts by weight of polyethylene glycol (PEG 4000), 2 parts by weight of processing aid (Structor WB212 manufactured by Sil + Seilach), and 1 part by weight of 2-mercaptobenzimidazole (Sumitomo) Chemical company Sumilyzer MB) was kneaded with a Banbury mixer to obtain a kneaded product. In the kneading, the temperature of the Banbury mixer at the start of kneading was 80 ° C., the rotor rotation speed was 60 rpm, and the kneading time was 5 minutes.

Process (2)
5 parts by weight of α, α′-bis (t-butylperoxy) diisopropylbenzene (60% of Peroximon F (40) active ingredient manufactured by NOF Corporation) per 100 parts by weight of EPDM-A in the kneaded product , 0.5 parts by weight of sulfur, a pair of 8 inch rolls with a roll temperature of 50 ° C., and an open roll (manufactured by Kansai Roll Co., Ltd.) with a roll gap of 4 mm, a front roll of 15 rpm, a back roll of 18 rpm The polymer composition was kneaded while being wound on the back roll side under the conditions described above, and the roll kneading processability of the polymer composition was evaluated. Next, the extrudability of the polymer composition was evaluated. The evaluation results are shown in Table 1.

Example 2
(Preparation of copolymer)
The temperature of a stainless steel polymerization tank equipped with a stirrer is kept at 60 ° C., and 1.13 kg / (hr · L) of hexane and 30.0 g of ethylene per unit time / unit volume of the polymerization tank. / (Hr · L), propylene was supplied at a rate of 160 g / (hr · L). VOCl ₃ was supplied to the polymerization tank at a rate of 266 mg / (hr · L), ethylaluminum sesquichloride (EASC) at 399 mg / (hr · L), and hydrogen at a rate of 0.001 NL / (hr · L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 9.2 g / (hr · L).
The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant. The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-B).
When EPDM-B was analyzed, the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-B was 0.62 / 0.38, and the iodine value was 25.1 (g / 100 g polymer). Mz / Mn was 17.4, Mw / Mn was 4.0, intrinsic viscosity was 1.41 dl / g, and tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) was 1.51.

(Preparation of polymer composition)
A polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-B was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated. The evaluation results of the polymer composition are shown in Table 1.

Comparative Example 1
(Preparation of copolymer)
In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 60 ° C., 0.458 kg / (hr · L) of hexane and 32.3 g / (hr · L) of ethylene per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr · L). VOCl3 was supplied to the polymerization tank at a rate of 140 mg / (hr · L), ethylaluminum sesquichloride (EASC) at 307 mg / (hr · L), and hydrogen at a rate of 0.010 NL / (hr · L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 1.9 g / (hr · L).
The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant.
The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-C).
When EPDM-C was analyzed, the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-C was 0.61 / 0.39, and the iodine value was 9.6 (g / 100 g polymer). Mz / Mn was 13.4, Mw / Mn was 3.8, intrinsic viscosity was 1.75 dl / g, and tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) was 1.65.

(Preparation of polymer composition)
A polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-C was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated. The evaluation results of the polymer composition are shown in Table 1.

Comparative Example 2
(Preparation of copolymer)
In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 55 ° C., 0.458 kg / (hr · L) of hexane and 32.4 g / (hr · L) of hexane per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr · L). VOCl 3 was supplied to the polymerization tank at a rate of 108 mg / (hr · L), ethylaluminum sesquichloride (EASC) at 237 mg / (hr · L), and hydrogen at a rate of 0.028 NL / (hr · L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 1.9 g / (hr · L).
The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant.
The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-D).
When EPDM-D was analyzed, ethylene unit amount / propylene unit amount (molar ratio) of EPDM-D was 0.61 / 0.39, iodine value was 10.3 (g / 100 g polymer), Mz / Mn was 11.5, Mw / Mn was 3.2, intrinsic viscosity was 1.65 dl / g, and tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) was 1.96.

(Preparation of polymer composition)
A polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-D was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated. The evaluation results of the polymer composition are shown in Table 1.

Comparative Example 3
(Preparation of copolymer)
In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 45 ° C., 0.458 kg / (hr · L) of hexane and 32.3 g / (hr · L) of ethylene per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr · L). VOCl3 was supplied to the polymerization tank at a rate of 58.4 mg / (hr · L), ethylaluminum sesquichloride (EASC) at 128 mg / (hr · L), and hydrogen at a rate of 0.076 NL / (hr · L). Further, dicyclopentadiene was supplied to the polymerization tank at a rate of 2.1 g / (hr · L).
The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant.
The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-E).
When EPDM-E was analyzed, the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-E was 0.62 / 0.38, and the iodine value was 9.5 (g / 100 g polymer). Mz / Mn was 10.6, Mw / Mn was 3.4, intrinsic viscosity was 1.52 dl / g, and tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm) was 1.78.

(Preparation of polymer composition)
A polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-E was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated. The evaluation results of the polymer composition are shown in Table 1.

Claims (2)

An ethylene-α-olefin-nonconjugated polyene copolymer satisfying the following requirements (A), (B), (C), (D) and (E).
(A): Intrinsic viscosity [η] is 0.5 to 1.8 dl / g.
(B): When the total content of the ethylene unit and the α-olefin unit is 100 mol%, the ethylene unit content is 50 to 90 mol%, and the α-olefin unit content is 50 to 10 mol%.
(C): The iodine value is 1-50.
(D): The ratio of tan δ at 100 ° C. and 2 cpm (tan δ (100 ° C., 2 cpm) / tan δ (100 ° C., 1000 cpm)) to tan δ at 100 ° C. and 1000 cpm is 1.0 to 1.7.
(E): The ratio of the Z-average molecular weight to the number average molecular weight (Mz / Mn) is 15 to 25, and the ratio of the weight average molecular weight to the number average molecular weight is 3 to 5.   The ethylene- of claim 1, wherein the α-olefin is propylene, and the non-conjugated polyene is at least one compound selected from the group consisting of 5-alkylidene-2-norbornene and 5-alkenyl-2-norbornene. α-olefin-nonconjugated polyene copolymer.